Hydrazine Radiolysis by Gamma-Ray in the N2H4–Cu+–HNO3 System

Radiolysis of chemical agents occurs during the decontamination of nuclear power plants. The γ-ray irradiation tests of the N₂H₄–Cu⁺–HNO₃ solution, a decontamination agent, were performed to investigate the effect of Cu⁺ ion and HNO₃ on N₂H₄ decomposition using a Co-60 high-dose irradiator. After the irradiation, the residues of N₂H₄ decomposition were analyzed by Ultraviolet-visible (UV) spectroscopy. NH₄⁺ ions generated from N₂H₄ radiolysis were analyzed by ion chromatography. Based on the results, the decomposition mechanism of N₂H₄ in the N₂H₄–Cu⁺–HNO₃ solution under γ-ray irradiation condition was derived. Cu⁺ ions form Cu⁺N₂H₄ complexes with N₂H₄, and then N₂H₄ is decomposed into intermediates. H⁺ ions and H^● radicals generated from the reaction between H⁺ ion and e_aq⁻ increased the N₂H₄ decomposition reaction. NO₃⁻ ions promoted the N₂H₄ decomposition by providing additional reaction paths: (1) the reaction between NO₃⁻ ions and N₂H₄^●+, and (2) the reaction between NO^● radical, which is the radiolysis product of NO₃⁻ ion, and N₂H₅⁺. Finally, the radiolytic decomposition mechanism of N₂H₄ obtained in the N₂H₄–Cu⁺–HNO₃ was schematically suggested.     

Electron Holes in G-Quadruplexes: The Role of Adenine Ending Groups

The study deals with four-stranded DNA structures (G-Quadruplexes), known to undergo ionization upon direct absorption of low-energy UV photons. Combining quantum chemistry calculations and time-resolved absorption spectroscopy with 266 nm excitation, it focuses on the electron holes generated in tetramolecular systems with adenine groups at the ends. Our computations show that the electron hole is placed in a single guanine site, whose location depends on the position of the adenines at the 3′ or 5′ ends. This position also affects significantly the electronic absorption spectrum of (G⁺)^● radical cations. Their decay is highly anisotropic, composed of a fast process (<2 µs), followed by a slower one occurring in ~20 µs. On the one hand, they undergo deprotonation to (G-H2)^● radicals and, on the other, they give rise to a reaction product absorbing in the 300–500 nm spectral domain.     

Electron-Induced Repair of 2′-Deoxyribose Sugar Radicals in DNA: A Density Functional Theory (DFT) Study

In this work, we used ωB97XD density functional and 6-31++G** basis set to study the structure, electron affinity, populations via Boltzmann distribution, and one-electron reduction potentials (E°) of 2′-deoxyribose sugar radicals in aqueous phase by considering 2′-deoxyguanosine and 2′-deoxythymidine as a model of DNA. The calculation predicted the relative stability of sugar radicals in the order C4′^• > C1′^• > C5′^• > C3′^• > C2′^•. The Boltzmann distribution populations based on the relative stability of the sugar radicals were not those found for ionizing radiation or OH-radical attack and are good evidence the kinetic mechanisms of the processes drive the products formed. The adiabatic electron affinities of these sugar radicals were in the range 2.6–3.3 eV which is higher than the canonical DNA bases. The sugar radicals reduction potentials (E°) without protonation (−1.8 to −1.2 V) were also significantly higher than the bases. Thus the sugar radicals will be far more readily reduced by solvated electrons than the DNA bases. In the aqueous phase, these one-electron reduced sugar radicals (anions) are protonated from solvent and thus are efficiently repaired via the “electron-induced proton transfer mechanism”. The calculation shows that, in comparison to efficient repair of sugar radicals by the electron-induced proton transfer mechanism, the repair of the cyclopurine lesion, 5′,8-cyclo-2′-dG, would involve a substantial barrier.     

Study of the coupling reactions between electrochemically generated aromatic radical anions and methyl, alkyl and benzyl radicals

Alkyl radicals produced in the indirect reduction of alkyl halides or alkyldimethylsulfonium salts by electrochemically generated aromatic radical anions couple fast with the latter and alkylated or dialkylated dihydro compounds are formed. Rate constants measured for the coupling reaction between on one hand methyl, primary, secondary and tertiary alkyl radicals as well as benzyl and cumyl radicals and on the other hand a wide spectrum of electrochemically generated aromatic radical anions are found to be about 1×10⁹ M⁻¹ s⁻¹. Previous measurements of coupling rate constants for primary alkyl radicals have been re-evaluated since they were affected by the presence of an S_N2 reaction occurring between the alkyl halides used as radical precursors and the aromatic radical anions. New experiments are also included using alkyldimethylsulfonium salts as precursors in order to prevent such S_N2 artefacts. It is concluded that sterical hindrance does not play a significant role for the radical-radical anion coupling reactions. In general the rate constants for the coupling reactions are all close to 10⁹ M⁻¹ s⁻¹.     

NO● Represses the Oxygenation of Arachidonoyl PE by 15LOX/PEBP1: Mechanism and Role in Ferroptosis

We recently discovered an anti-ferroptotic mechanism inherent to M1 macrophages whereby high levels of NO^● suppressed ferroptosis via inhibition of hydroperoxy-eicosatetraenoyl-phosphatidylethanolamine (HpETE-PE) production by 15-lipoxygenase (15LOX) complexed with PE-binding protein 1 (PEBP1). However, the mechanism of NO^● interference with 15LOX/PEBP1 activity remained unclear. Here, we use a biochemical model of recombinant 15LOX-2 complexed with PEBP1, LC-MS redox lipidomics, and structure-based modeling and simulations to uncover the mechanism through which NO^● suppresses ETE-PE oxidation. Our study reveals that O₂ and NO^● use the same entry pores and channels connecting to 15LOX-2 catalytic site, resulting in a competition for the catalytic site. We identified residues that direct O₂ and NO^● to the catalytic site, as well as those stabilizing the esterified ETE-PE phospholipid tail. The functional significance of these residues is supported by in silico saturation mutagenesis. We detected nitrosylated PE species in a biochemical system consisting of 15LOX-2/PEBP1 and NO^● donor and in RAW264.7 M2 macrophages treated with ferroptosis-inducer RSL3 in the presence of NO^●, in further support of the ability of NO^● to diffuse to, and react at, the 15LOX-2 catalytic site. The results provide first insights into the molecular mechanism of repression of the ferroptotic Hp-ETE-PE production by NO^●.     

Oxidative Degradation of Thiaproline Derivatives in Aqueous Solutions Induced by •OH Radicals

The participation of neighboring amino and carboxyl groups in thiazolidyne-4-carboxylic acid (thiaproline) and its two derivatives, thiazolidyne-2-carboxylic acid and thiazolidyne-2,4-dicarboxylic acid, is demonstrated during ^.OH-radical-induced oxidation in aqueous solutions. The reaction of ^.OH radicals with these compounds does not lead to the expected one-electron oxidized sulfur-centered radical cations and subsequently to the intermolecularly (S∴S)-bonded dimeric radical cations (even at very high concentration of thiaprolines (>50 mM )), but rather to the elimination of CO₂ with the parallel formation of αN radicals. The latter radicals formed in thiaproline and thiazolidyne-2,4-dicarboxylic acid subsequently undergo β-fragmentation of the C S bond, leading to the thiyl radicals (RS^.). The αN and RS^. radicals were probed and quantified by one-electron reduction of p-nitroacetophenone (PNAP) and by one-electron oxidation of the monoanion of ascorbic acid (AH⁻), respectively. The calculated stabilization enthalpies of the αN radicals show that the loss of CO₂ is thermodynamically a favorable process. The Gibbs free energies of β-fragmentation processes in thiaproline and thiazolidyne-2,4-dicarboxylic acid are equal to −3.7 and −10.2 kJ mol⁻¹, respectively, showing that at room temperature both are exergonic. A general ^.OH-radical-induced oxidation mechanism of thiaproline derivatives in aqueous solutions is proposed.     

FeIII,CuII and ZnII Complexes of the Rigid 9-Oxido-phenalenone Ligand—Spectroscopy,Electrochemistry, and Cytotoxic Properties

The three complexes [Fe(opo)₃], [Cu(opo)₂], and [Zn(opo)₂] containing the non-innocent anionic ligand opo⁻ (opo⁻ = 9-oxido-phenalenone, Hopo = 9-hydroxyphenalonone) were synthesised from the corresponding acetylacetonates. [Zn(opo)₂] was characterised using ¹H nuclear magnetic resonance (NMR) spectroscopy, the paramagnetic [Fe(opo)₃] and [Cu(opo)₂] by electron paramagnetic resonance (EPR) spectroscopy. While the EPR spectra of [Cu(opo)₂] and [Cu(acac)₂] in dimethylformamide (DMF) solution are very similar, a rather narrow spectrum was observed for [Fe(opo)₃] in tetrahydrofuran (THF) solution in contrast to the very broad spectrum of [Fe(acac)₃] in THF (Hacac = acetylacetone, 2,4-pentanedione; acac⁻ = acetylacetonate). The narrow, completely isotropic signal of [Fe(opo)₃] disagrees with a metal-centred S = 5/2 spin system that is observed in the solid state. We assume spin-delocalisation to the opo ligand in the sense of an opo⁻ to Fe^III electron transfer. All compounds show several electrochemical opo-centred reduction waves in the range of −1 to −3 V vs. the ferrocene/ferrocenium couple. However, for Cu^II and Fe^III the very first one-electron reductions are metal-centred. Electronic absorption in the UV to vis range are due to π–π* transitions in the opo core, giving Hopo and [Zn(opo)₂] a yellow to orange colour. The structured bands ranging from 400 to 500 for all compounds are assigned to the lowest energy π−π* transitions. They show markedly higher intensities and slight shifts for the Cu^II (brown) and Fe^III (red) complexes and we assume admixing metal contributions (MLCT for Cu^II, LMCT for Fe^III). For both complexes long-wavelength absorptions assignable to d–d transitions were detected. Detailed spectroelectrochemical experiments confirm both the electrochemical and the optical assignments. Hopo and the complexes [Cu(opo)₂], [Zn(opo)₂], and [Fe(opo)₃] show antiproliferative activities against HT-29 (colon cancer) and MCF-7 (breast cancer) cell lines in the range of a few µM, comparable to cisplatin under the same conditions.     

The photoelectrochemical reduction of pyrene in acetonitrile solution

The reduction of pyrene (Py) at a mercury channel electrode is studied in acetonitrile solution, both in the dark and under conditions where the pyrene radical anion (Py^−.) is photoexcited, using a wavelength of 501.7 nm. In the dark a reversible one-electron process occurs forming the radical anion. However, upon photoexcitation of the electrogenerated radical anion, photocurrents are observed, and the precise electrode mechanism is shown to be: The photocurrent arising from further reduction of Py, since rapid homogeneous reactions of Py⁻² give electroinactive products. With this scheme an “effective” second order decay of Py^−√ is observed, RATE = −k_eff[Py^−√]^p2 where k_eff is proportional to k₃ I/k_f. k_eff has been evaluated from analysis of the limiting current-flow rate behaviour at the channel electrode at the channel electrode. This was found to be 4.0 ± 0.1 × 10³ mol−1 dm³ s⁻¹ at a light intensity of 0.30 W cm⁻² and a pyrene concentyration of 2.97 mM.     

Electrochemical oxidation of aliphatic hydrocarbons promoted by inorganic radicals. II. NO3 radicals

The anodic electrolysis of linear alkanes in tert-butanol/H₂O solutions containing HNO₃ and saturated with oxygen at P_{O 2}=1 atm results in the partial oxidation of the hydrocarbons to the corresponding isomeric ketones. The experimental data are in support of a mechanism in which the first steps are: (1) one-electron transfer from the nitrate ion to the anode to give a nitrate radical; (2) hydrogen abstraction by the nitrate radical on the aliphatic substrate to give an alkyl radical; (3) molecular oxygen addition by the alkyl radical and formation of peroxy radicals. These species decay by bimolecular reactions and a carbonyl function is formed. The isomer distribution is in excellent accord with a statistical H abstraction from the secondary C–H bonds.     

The Chemical Background of Advanced Oxidation Processes

In advanced oxidation processes, the hydroxyl radical is the main initiator of the degradation of pollutants. For aromatic molecules, the rate coefficients are between 2×10⁹ and 1×10¹⁰ mol⁻¹ dm³ s⁻¹ and show some variation according to the electron-withdrawing or donating nature of the substituents. The one-electron oxidant ^.OH induces 2–4 electron oxidations of many aromatic pollutants. These high rates are explained by ^.OH addition to an unsaturated bond, scavenging of the organic radical by dissolved O₂, and subsequent reactions. In amino-substituted molecules and in azo dyes the efficiency is lower, because O₂ cannot compete efficiently with the unimolecular transformation of carbon-centered radicals. Generally, the toxicity first increases and then decreases with treatment time. The increase is attributed to the high toxicity of some degradation products and to H₂O₂ formation. In surface waters, traces of transition metal ions degrade some of the H₂O₂ in Fenton-like processes.     

Unique Regulation of Intestinal Villus Epithelial Cl−/HCO3− Exchange by Cyclooxygenase Pathway Metabolites of Arachidonic Acid in a Mouse Model of Spontaneous Ileitis

Electrolytes (NaCl) and fluid malabsorption cause diarrhea in inflammatory bowel disease (IBD). Coupled NaCl absorption, mediated by Na⁺/H⁺ and Cl⁻/HCO₃⁻ exchanges on the intestinal villus cells brush border membrane (BBM), is inhibited in IBD. Arachidonic acid metabolites (AAMs) formed via cyclooxygenase (COX) or lipoxygenase (LOX) pathways are elevated in IBD. However, their effects on NaCl absorption are not known. We treated SAMP1/YitFc (SAMP1) mice, a model of spontaneous ileitis resembling human IBD, with Arachidonyl Trifluoro Methylketone (ATMK, AAM inhibitor), or with piroxicam or MK-886, to inhibit COX or LOX pathways, respectively. Cl⁻/HCO₃⁻ exchange, measured as DIDS-sensitive ³⁶Cl uptake, was significantly inhibited in villus cells and BBM vesicles of SAMP1 mice compared to AKR/J controls, an effect reversed by ATMK. Piroxicam, but not MK-886, also reversed the inhibition. Kinetic studies showed that inhibition was secondary to altered K_m with no effects on V_max. Whole cell or BBM protein levels of Down-Regulated in Adenoma (SLC26A3) and putative anion transporter-1 (SLC26A6), the two key BBM Cl⁻/HCO₃⁻ exchangers, were unaltered. Thus, inhibition of villus cell Cl⁻/HCO₃⁻ exchange by COX pathway AAMs, such as prostaglandins, via reducing the affinity of the exchanger for Cl⁻, and thereby causing NaCl malabsorption, could significantly contribute to IBD-associated diarrhea.     

Preparation of a Facilitated Transport Membrane Composed of Carboxymethyl Chitosan and Polyethylenimine for CO2/N2 Separation

The miscibility of carboxymethyl chitosan/polyethylenimine (CMCS/PEI) blends was analyzed by FT-IR, TGA and SEM. Defect-free CMCS/PEI blend membranes were prepared with polysulfone (PSf) ultrafiltration membranes as support layer for the separation of CO₂/N₂ mixtures. The results demonstrate that the CMCS/PEI blend is miscible, due to the hydrogen bonding interaction between the two targeted polymers. For the blended membrane without water, the permeability of CO₂ gas is 3.6 × 10⁻⁷ cm³ cm⁻² s⁻¹ cmHg⁻¹ and the corresponding separation factor for CO₂ and N₂ gas is about 33 at the pressure of 15.2 cmHg. Meanwhile, the blended membrane with water has the better permselectivity. The blended membrane containing water with PEI content of 30 wt% has the permeance of 6.3 × 10⁻⁴ cm³ cm⁻² s⁻¹ cmHg⁻¹ for CO₂ gas and a separation factor of 325 for CO₂/N₂ mixtures at the same feed pressure. This indicates that the CO₂ separation performance of the CMCS/PEI blend membrane is higher than that of other facilitated transport membranes reported for CO₂/N₂ mixture separation.     

Reaction of N-Acetylcysteine with Cu2+: Appearance of Intermediates with High Free Radical Scavenging Activity: Implications for Anti-/Pro-Oxidant Properties of Thiols

We studied the kinetics of the reaction of N-acetyl-l-cysteine (NAC or RSH) with cupric ions at an equimolar ratio of the reactants in aqueous acid solution (pH 1.4–2) using UV/Vis absorption and circular dichroism (CD) spectroscopies. Cu²⁺ showed a strong catalytic effect on the 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonate) radical (ABTSr) consumption and autoxidation of NAC. Difference spectra revealed the formation of intermediates with absorption maxima at 233 and 302 nm (ε₃₀₂/Cu > 8 × 10³ M⁻¹ cm⁻¹) and two positive Cotton effects centered at 284 and 302 nm. These intermediates accumulate during the first, O₂-independent, phase of the NAC autoxidation. The autocatalytic production of another chiral intermediate, characterized by two positive Cotton effects at 280 and 333 nm and an intense negative one at 305 nm, was observed in the second reaction phase. The intermediates are rapidly oxidized by added ABTSr; otherwise, they are stable for hours in the reaction solution, undergoing a slow pH- and O₂-dependent photosensitive decay. The kinetic and spectral data are consistent with proposed structures of the intermediates as disulfide-bridged dicopper(I) complexes of types cis-/trans-Cu^I₂(RS)₂(RSSR) and Cu^I₂(RSSR)₂. The electronic transitions observed in the UV/Vis and CD spectra are tentatively attributed to Cu(I) → disulfide charge transfer with an interaction of the transition dipole moments (exciton coupling). The catalytic activity of the intermediates as potential O₂ activators via Cu(II) peroxo-complexes is discussed. A mechanism for autocatalytic oxidation of Cu(I)–thiolates promoted by a growing electronically coupled –[Cu^I₂(RSSR)]_n– polymer is suggested. The obtained results are in line with other reported observations regarding copper-catalyzed autoxidation of thiols and provide new insight into these complicated, not yet fully understood systems. The proposed hypotheses point to the importance of the Cu(I)–disulfide interaction, which may have a profound impact on biological systems.     

Synthesis of 2-Acyloxycyclohexylsulfonamides and Evaluation on Their Fungicidal Activity

Eighteen N-substituted phenyl-2-acyloxycyclohexylsulfonamides (III) were designed and synthesized by the reaction of N-substituted phenyl-2-hydroxyl-cycloalkylsulfonamides (I, R¹) with acyl chloride (II, R²) in dichloromethane under the catalysis of TMEDA and molecular sieve. High fungicidal active compound N-(2,4,5-trichlorophenyl)-2-(2-ethoxyacetoxy) cyclohexylsulfonamide (III-18) was screened out. Mycelia growth assay against the Botrytis cinerea exhibited that EC₅₀ and EC₈₀ of compound III-18 were 4.17 and 17.15 μg mL⁻¹ respectively, which was better than the commercial fungicide procymidone (EC₅₀ = 4.46 μg mL⁻¹ and EC₈₀ = 35.02 μg mL⁻¹). For in vivo activity against B. cinerea in living leaf of cucumber, the control effect of compound III-18 was better than the fungicide cyprodinil. In addition, this new compound had broader fungicidal spectra than chlorothalonil.     

Electron-Induced Decomposition of Uracil-5-yl O-(N,N-dimethylsulfamate): Role of Methylation in Molecular Stability

The incorporation of modified uracil derivatives into DNA leads to the formation of radical species that induce DNA damage. Molecules of this class have been suggested as radiosensitizers and are still under investigation. In this study, we present the results of dissociative electron attachment to uracil-5-yl O-(N,N-dimethylsulfamate) in the gas phase. We observed the formation of 10 fragment anions in the studied range of electron energies from 0–12 eV. Most of the anions were predominantly formed at the electron energy of about 0 eV. The fragmentation paths were analogous to those observed in uracil-5-yl O-sulfamate, i.e., the methylation did not affect certain bond cleavages (O-C, S-O and S-N), although relative intensities differed. The experimental results are supported by quantum chemical calculations performed at the M06-2X/aug-cc-pVTZ level of theory. Furthermore, a resonance stabilization method was used to theoretically predict the resonance positions of the fragment anions O⁻ and CH₃⁻.     

Experimental and Theoretical Study of N2 Adsorption on Hydrogenated Y2C4H− and Dehydrogenated Y2C4− Cluster Anions at Room Temperature

The adsorption of atmospheric dinitrogen (N₂) on transition metal sites is an important topic in chemistry, which is regarded as the prerequisite for the activation of robust N≡N bonds in biological and industrial fields. Metal hydride bonds play an important part in the adsorption of N₂, while the role of hydrogen has not been comprehensively studied. Herein, we report the N₂ adsorption on the well-defined Y₂C₄H_0,1⁻ cluster anions under mild conditions by using mass spectrometry and density functional theory calculations. The mass spectrometry results reveal that the reactivity of N₂ adsorption on Y₂C₄H⁻ is 50 times higher than that on Y₂C₄⁻ clusters. Further analysis reveals the important role of the H atom: (1) the presence of the H atom modifies the charge distribution of the Y₂C₄H⁻ anion; (2) the approach of N₂ to Y₂C₄H⁻ is more favorable kinetically compared to that to Y₂C₄⁻; and (3) a natural charge analysis shows that two Y atoms and one Y atom are the major electron donors in the Y₂C₄⁻ and Y₂C₄H⁻ anion clusters, respectively. This work provides new clues to the rational design of TM-based catalysts by efficiently doping hydrogen atoms to modulate the reactivity towards N₂.     

Estimation of standard reduction potentials of alkyl radicals involved in atom transfer radical polymerization

The redox properties of some alkyl radicals, which are important in atom transfer radical polymerization both as initiators and mimics of the propagating radical chains, have been investigated in CH₃CN by an indirect electrochemical method based on homogeneous redox catalysis involving alkyl halides (RX) and electrogenerated aromatic or heteroaromatic radical anions (D⁻). Dissociative electron transfer between RX and D⁻ yields an intermediate radical (R), which further reacts with D⁻ either by radical coupling or by electron transfer. Examination of the competition between these reactions, which depends on ED/D−°, allows determination of the standard reduction potential of R as well as the self-exchange reorganization energy λR/R⁻. The standard reduction potentials obtained for the radicals CH₂CN, CH₂CO₂Et and CH(CH₃)CO₂Me are −0.72 ± 0.06, −0.63 ± 0.07 and −0.66 ± 0.07 V vs. SCE, respectively. Quite high values of λR/R⁻ (from 122 to 164 kJ mol⁻¹) were found for all radicals, indicating that a significant change of structure accompanies electron transfer to R.     

ATRP poly(acrylate) star formation: A comparative study between MALDI and ESI mass spectrometry

Optimised matrix-assisted laser desorption/ionisation (MALDI) and electrospray ionisation (ESI) mass spectrometry (MS) methodologies were systematically compared in terms of their relative abilities to identify distinct chemical species present in samples associated with a polymer mechanistic study. In order to perform the investigation, formation processes involved in atom transfer radical polymerisation (ATRP) mediated methyl acrylate (MA) star polymerisations were studied. In addition to the 4-armed ATRP initiator employed in the polymerisations, initiator side-products were found to generate oligomeric chains. At a relatively high monomer to polymer conversion, terminal Br loss was observed in these oligomers; this Br loss was hypothesised to occur via degradative transfer reactions involving the radicals (CH₃)₂?OH, ?H₃ and ?H₂COCH₃, which were derived from the acetone used as a solvent in the polymerisations, as well as hydrogen radicals donated by the ligand N,N′,N′,N″,N″-pentamethyldiethylenetriamine (PMDETA). In performing these studies, ESI was found to identify a greater number of distinct chemical species in the samples under investigation when compared to the employed MALDI technique, suggesting that the utilisation of ESI must be strongly considered in polymer mechanistic investigations if the maximum number of end-group functionalities within a given polymer sample are to be identified.